Monopyridinium derivatives of esters of oxyalkylated diphenylol methanes



Patented Aug. 1, 1950 MONOPYRIDINIUM DERIVATIVES OF ES- TERS OF OXYALKYLATED DIPHENYLOL METHANES Melvin De Groote, University 'City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd, Wilmington, Del., a corporation of Delaware 1 No Drawing. Original application April 2, 1945,

Serial No. 586,267. Divided and this application November 26, 1945, Serial No. 630,974

Claims.

This invention relates to a new chemical compound or product, and to the manufacture of same, our present application being a division of our pending application Serial No. 586,267, filed April2, 1945, now Patent No. 2,430,001. One object of our invention is to provide a new material or composition of matter, that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions, but which is also capable of use for various other purposes, or in various other arts.

Another object of our invention is to provide a practicable method for manufacturing or producing the new material or composition of matter above referred to.

The new material or composition of matter herein described, consists of a hydrophile acylated pyridinium compound of the formula:

in which R5 isa radical selected from the class consisting of methylene and hydrocarbon substituted methylene radicals having not over '7 car- M bon atoms; R is the radical obtained by the removal of an alpha-hydrogen atom from the acid radical of a low molecular weight monocarboxy acid ester of a phenoxyalkanol of the formula:

R1O(R2O)11H in which R1 is a substituted monocyclic phenyl radical having 2 of the 3 reactive 2, 4, 6 positions substituted by 2 alkyl side chains, of which at least one contains at least 3 carbon atoms, and

the longest of which does not contain more than 8 carbon atoms; R20 is an alkoxy radical selected from the group consisting of -C2H4O and C3Hs0 radicals; and n is a small whole numrepeating the previous example with specific reference to chloroacetic acid, the formula becomes:

The herein contemplated procedure involves steps which .converta water-insoluble chemical compound into a hydrophile or water-miscible compound by conversion into a pyridinium salt. In some instances, it may be necessary to use enough oxyalkylating agent that n may be as much as 6 or 8, instead of being limited to 8, in order to insure water solubility. Furthermore, it will be subsequently shown that one may conveniently react a diol of the kind contemplated as a reactant, with one mole of the monocarboxy acid, such as oleic acid, ricinoleic acid, naphthenic acid, or the like, and then subsequently oxyalkylate again prior to esterification, with chloroacetic acid.

Briefly stated, the preparation of our new material or composition of matter contemplates five steps: The first step consists in reacting 2 moles of a properly selected substituted phenol with one mole of an aldehyde, so as to produce a diphenylolmethaneor substituted methane. The preferredaldehyde is formaldehyde, on account of its reactivity and low cost. Other aldehydes which may be used are acetaldehyde, propionaldehyde, butyraldehyde, and furfural. The condensation reactions of this type are well known and do not require description. In the case of furfural, it is desirable to use alkaline condensing agents, but in the other instances, acid or acidic substances are usually employed. Since these condensation reactions cannot produce resins in the usual sense, they are comparatively simple and result in oils varying from moderately viscous substances to oils so viscous as to appear to be almost solid.

The phenols are selected so that resinification does not take place, insofar that the phenols are limited to types in which there is only one reactive nuclear hydrogen atom. Specifically, then, the phenols may be indicated by the following formula:

More specifically, then, R in the first formula H of the text represents the divalent radical by 0 elimination of a nuclear hydrogen atom and a halogen from the ester of the formula: 811ml in which all of the symbols have their prior significance and OCRS Halogen is the acyl radical of a lowmolecular weight alphachloromonocarboxy with the proviso that the two alkyl groups occupy 2 of the 2, 4, 6 positions, and that at least one of the alkyl side chains contains at least three carbon atoms, and the longest alkyl side chain does h n atoms d must e r ne o the not contain more than 8 carbon atoms. When 2 moles of such phenol are condensed in the customary manner with a reactive aldehyde, one obtains a substituted diphenylol methane or substi: tuted methane of the following formula? 2-4-diarnyl phenol or p-tert-butyl-o-cresol. Other suitable phenols include U- 5- Pa ent 973 25 da e Me h 16, 37 e R he et el-v Se lsov U. Pa ent Ne- 24 0 150 ated Febr a 1 38. 9 ttle t Other phenols can be prepared by the allgylathe of h er areere e b th Sa hfe du eet i mnlq ed e the a l y at h hehelsee.- 1- Patent IQ- a069 dat d Novembe 19,1935, to Hester.

W have h he 2 .i-d r p phen i a s a e 1 n w meter al.-, Se lse U Pate t h 1 2 8 ed D t mb r 1936. 29 ar- Pehter; 2 1 %1 dated Janua 4, .93 to 13119; an 2 2 753. t Me l da ed J ly 6, 1940.

It is, understood that there is no objection to hel re en e of a ddit on l e s l r iee i re- -r ded hat s hee s ill lea es a r a tiv thieer hydrogen at m Seth el edit a. if present, is, limited to radicals having not over e h s eh For all racti al ur oses. ho ever, such compounds are derived from metacresol or similar homologs, and thus, for the sake of brevity in the hereto, appended claims, such alkyl groups will be indicated as being either he 3 Q$ IL er in th 5; r ei iq H e e it s unde s ha he a d, 5 esitie e a obvious equivalents. One such" example would be the product obtained by the propylation of metacresol. The meta group does not occupy a reactive position, and its presence does not interfere with the subsequent reaction. In a few instances, compounds are obtainable where a cyclic radical may serve instead of an alkyl radical, for example, in 4-'tertebutyl-2-phenylphenol or 4-tert-butyl-2-cyclohexylphenol.

Since the substituted phenols employed as re--,

actants are invariably water-insoluble, and since tormalde de, a w er-sol ble alde y e, s: the preferred reactant for introducing the methylene bridge, or its equivalent, we havev found it most desirable to employ the procedure described in,

U. S. Patent No. 2,330,217, dated September 28, 1943, to Hunn. Briefly stated, this procedure incl de th use f an id. cata yst alon with an emulsifying agent to promote emulsifieation, and thus, reaction between the Water-insoluble phenol and the Water-soluble aldehyde. As an example of such procedure, the following is ineluded:-

Pnuuop r p HYDE CONDENSATION Example 1 Pounds Di mvl 2 phenol 702 Formalin 40% U. S. P. 114 Concentrated hydrochloric acid 3.3

Allrylated aryl sulfonic acid salt (Nacconal N. R. S. F.) 3.3

PHENOL ALDEHY QQNJQENSAQQN Example 2 The same procedure is employed as the. previous example, except that 613 pounds of dipropyl (2, 4), phenol replaces the 702; pounds of diamylphehel used in the r ce ng ample- PH-ENOL ALDIIEJI-lY-DE GONDENSATION Em r e 3 The same procedure is followed as in the two previous examples, except that one uses a mixture consisting of 351 pounds of diamyl (2,4) phenol and 309 pounds of dipropyl (2,4) phenol. The result of such mixture is that the condensate is also a mixture, of which OXlQ-rthil'd' corresponds to Example 1, preceding, one-third to Example 2 preceding, and the remaining third represents the type of compound in which the phenol nuclei are different, one. being an amylated nucleus and the other a propylated nucleus.

Due to ready availability, and other desirable properties, it is particularly convenient and economical to replace dipropyl (2,4) henol with an equivalent amount of 4,6-di-tertiary-butylm-cresol which is indicated by the following formula:

. satin-6H,,

Inst ad us th em ls fi ti h roced r ne may. o c se. m oy anoth l know method, to wit, the use of an alkaline catalyst in excess, particularly amounts sufiicient to dissolve or solubilize the water-insoluble phenol. Usually, a 10% sodium hydroxide solutionis used to dissolve the substituted phenol. For complete details see, for example, Industrial and Engineerins hem s r o m .0, 131 1. pa e. 10. 9,,v

f T alkyl- "In the second step a properly selected phenol of the kind typified by the formula:

H H O If one employs 2 moles of ethylene oxide, the

reaction may be indicated in the following manner:

Thethird step and the fourth step of the method for producing our new material or compound, consist in esterifying a compound of the kind described with a reactant of the kind pre- *firstand then subsequently with the high molecular weight monocarboxy acid. The reverse order may be followed, if desired, and particularly if the high molecular weight acid is not a hydroxylated acid, such as ricinoleic acid, hy- ,dr0xystearic acid, etc.

Thus, the third step consists in esterifying the "diol thus obtained with a suitable alpha-chloromonocarboxy acid, such as chloroacetic acid, to

form the corresponding ester. This reaction may ,'be illustrated in the following manner:

The fractional ester so obtained is then esteri- .fied with a high molecular weight monocarboxy acid such as a higher fatty acid, and particularly an unsaturated higher fatty acid so as to give 1a complete ester, as indicated in the following alkylalkylsubsequently specified. such reaction may he indicated in the following manner: oim ooonloao 5 alkylalkyl chlorine N"H2C.COOH4CO As suggested, one-may not "only use pyridine,

but other homologs of pyridine, that ispmembers of the pyridine series. For instance, members of the pyridine series suitableas reactants include pyridine, and methylated pyridines, i; e., pyridines, r in whichronc, 'two orthreemethyl groups have been substituted in'thenucleussuch as picolines, lutidines and collidines. :Coaltar bases represent mixtures of suitable heterocyclic materials which may be used as such; or after suitable purification, without separation into the individual components. i a

While chloroaceticacid or chloroacetyl chloride is the preferred halogen carboxylicw acid compound, other halogen acids, halogen substituted acyl halides,1a nd esterifying derivatives are suitable, particularly a-halogen carboxylic acids of not overqthree- Lcarbonatoms. When the halogen is inthe a-position to the group, the reaction seems to go with greater readiness. With the shorter chain esterifying halogen carboxylic acids or their functional equivalents, especially chloroacetyl chloride, the reaction goes with great ease. Other halogen acylating compounds which are suitable are, .for example, 40 a-chloropropionic acid, etc., but especiallyany acidoftheformula:

where R is a hydrogen atom or a methyl radical. Treatment of water insoluble phenols with alkylene oxides of the kind enumerated, i. e. with ethylene oxidenand propylene oxide, is a well known procedure. ;S u'ch compounds .are frequently oxyethylatedso as to render them watersoluble... In the present instance instead of treating one mole of the selected phenol withalarge ratio of oxyalkylating agent, one employs instead a comparatively low ratio, as indicated by. the value for the letter n in prior formulae, ..In other words, one treats the phenol with one mole, two moles or three moles of theoxyalkylating agent. The product so obtained is stilldistinctly waterinsoluble, and thisis also true-ofthe ester derived therefrom. It is to be noted, however that such water-insoluble product represents thefinitial oxyalkylation step. in the same type ofprocedure employed to produce -a watersoluble product. Thus, as anexample of various: patents which teach the oxyalkylationof water-insoluble phenols, including the stepwise addition of the oxyalkylating agent, attention is directed to. the following: British Patent No. 470,181, British Patent No. 452,366, US s: Patent No.2,2431330, 70 dated May 27, 1941, toDeGroote and Keiser, and U. S. Patent No. 2,233,381, dated February 25, 1941, to De' Groote and 'Keiser. Having obtained the water-insoluble Ibis(phenoxy-alkanol) methane, suchproduct is esterified with chloroacetyl chloride, chloroaceticacid, bromoacetic-ecid, alpha-ch ronronionic acid, or. th

.carboxy acids having 8. to. 32 carbon atoms. Obviously, one an use no only the acids, bu their: quivalents; uch as the anhydrides, acyl :chlorides, esters, etc- It is: well known that: certain monocarboxy acids containing 8: carbon atoms. or more, and not; more than 32 carbon atoms, are characterized by the fact: that they combine with alkalies to produce soap. or soap-like materials. These acids include ifatty acids, resin acids, petroleum acids, etc. In stead of fatty acids, one might employ the chlorinated fatty acids. Instead of the resin acids, one might employ the hydrogenated resin acids. In-

stead of naphthenic acids, one might employ brominated' naphthenic acids, etc.

The fatty acids. are of the, type commonly referred to. as higher fatty acids; and of course, this. is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum acids include not. only naturally-occurring naphtheni'c acids, but also acids obtained by the oxidation of: wax, paraffin, etc. Such acids may have as many as 32 carbon atoms. For instance, see U. S. Patent No. 2,242,837, dated May 20, 1941, to. Shields.

Although any of the monocarboxy acids having at least 8 and not more than 32 carbon atoms can be employed, it isour preference to employ the higher fatty acids, rather than petroleum acids, rosin acids, and the like. We have. found that by far-the most effective, demulsifying agents are obtained from unsaturated fatty acids having 18 carbon atoms. Such, unsaturated fatty acids include the higher fatty acids, such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. Cne may employ mixed, fatty acids, as, for example, the fatty acids, obtained by hydrolysis of cottonseed oil, soybean oil, corn oil, etc. When our new product or compound is; intended to be used as a demulsifier for resolving petroleum emulsions of the water-in-oil type, it is preferably obtained from fatty acids, and more specifisally, unsaturated fatty acids.

Having obtained the completely esteriiied diol, it is only necessary to react such compound with pyridine; or a C-linked methyl homolog of pyridine. This reaction takes place rapidl by refluxing in presence of an excess of'pyridine, and subsequently removing the excess of pyridine which does not enter the reaction by distillation, and

preferably, vacuum distillation. The herein described procedures are illustrated by the following ex mples Example 1' One pound moleof the product described under sodium methylate; as the reactionproceeds; the sodium methylate either dissolves or is converted into a soluble compound by chemical combination. Reaction is conducted at approximately 125 C. and -200 pound gauge pressure for approximately 2% to. 4 hours, until the reaction appears to be complete, asv indicated by the pressure dropping to zero. The product so obtained may be indicated by the following formula:

DI'tHYDROXYALKYLOXYPI-IENYL) METHANE Example 2 The same procedure is employed as in the preceding example, except that 4 pound moles of ethylene oxide are employed instead of 2 pound moles and the period of reaction is. approximately fifty percent longer.

DI HYDROXYALKYLORYPHENYL) METHANE Example 3 The same procedure is employed as in Example 1, preceding, except that 6 pound moles of ethylene oxide are employed instead of 2 pound moles and the time of reaction is, approximately twice that indicated, in Example 1 DI (HYDBOXYALK'YLOXYPHENYL METHANE Example 4 The same procedure is employed as in the three preceding examples, except that the propylated compound described under the heading Phenol Aldehyde Condensation, Example 2 is substituted for the amylated derivative employed in the three preceding examples.

DI (HYDROXYALKYLOXYPHENYL) Example 5 The same procedure is empioyed as in Examples 1 to 4, preceding. except that propylene oxide, is substituted for ethylene oxide.

Previous reference has been made to the fact that the esterification step is carried out in the conventional manner, preferably in the presence of an inert-solvent. This simply means that the reactants, to. Wit, the acid, such as chloroacetic acid, and the bisfiphenoxyalkanol) methane, are mixed in equimolar proportions in presence of a. solvent, in which both are soluble, such as xylene, cymene, decalin, or the like. The mixture is refluxed at some suitable temperature, above 100 C. and below 200, C., so that water of formation resulting from the esteriiication reaction is carried over as a constant boiling mixture. Such mixed vapor is condensed in the customary manner so the water is trapped off, measured and then discarded and; the solvent returned to the reaction vessel for further use. Ordinarily, such reactions are catalyzed by the; addition of an acidic catalyst, such as toluene sulfonic acid, an alkyl phosphoric acid, dry hydrochloric acid, trichloroacetic acid, or the like. Insofar that the alpha-chloroc'arboxy acids, show marked acidity, in comparison with the unchlorinated carboxy acids, the reactionv may be conducted without an added catalyst, if desired, or in the presence of an added catalyst, such as /2% to 1% of toluene sulfonic acid. Such catalyst tends to discolor the final product, but this is often immaterial.

aid-17,092

9'. as, for example, when the product is used as a demulsifier. The entire procedure is too well known to require further elaboration, but is illustrated by the following examples:

FRACTIONAL ESTER Example 1 The same procedure is followed as in the preceding example, except that the di hydroxyalkyloxyphenyDmethane, prepared as described under theheadings of Examples 2, 3, 4, and 5, are substituted for the compound employed in immediately preceding Example 1 FRACTIONAL ESTER Example 3 Y The same procedure is imployed as in the two preceding examples, except that a-chloropropionic acid is substituted for a-chloroacetic acid.

FRACTION AL ESTER Example 4 Chlo'roacetylchloride is substituted for the chloroacetic acid employed in Fractional Ester, Exampie 1. The reaction starts totake place rapidly between 45 C. and 80 C., and the temperature should be controlled so the .reaction takes place atthe lowest suitable temperature. The acylchloride should be added slowly. to the di(hydroxyalkyloxyphenyl) methane with constant and vigorous stirring. Hydrochloric, acid is; formed and should be vented and disposed ofin asuitable manner. If the reaction does not take place promptly, the temperature should be raised moderately, for instance, 5 to l5 C. or a bit higher, until the reaction proceeds smoothly However, as'soon as the reaction does start, the tempera-' ture should be lowered until the reaction pro-- ceeds at the slowestfeasible rate. Generally, this, means use of proper cooling devices or controlled slow addition of the acylchloride Completeness of the reaction can b determined in any suitable manner, such as a check on the amount ofhydrochloric acid eliminated, orthe drop in hydroxyl value of the reactant mixture. When the reaction is complete, anyhydroc'hloric acid gas dissolved in the reaction mass should be eliminated by passing an inert gas, suchas carbon dioxide, through the mixture.

. If, however, fractional esters of the kind exemplified by the present examples are not intended for, storage as anintermediate, then insofar that the next step, i.- e., the conversionlof a fractional ester into a complete ester Withthe introduction of a high molecular weight acyl group, is still the same sort of reaction, there is; no need to eliminate the catalyst or flush out the hydrochloric acid gas, if present. As a general rule, however, no catalyst is added, as chloroaceticacid is acidicenough to act as a catalyst itself.; For this reai- All son, our preference is to follow the procedure'in the previous examples, and assuming that there is no hydrochloric acid present, to simply add a; small amount of conventional catalyst, such as.

toluene sulfonic acid and alkyl phosphoric acid, or

the like,to the extent of about one-half of 1%, or.

thereabouts, and proceed in substantially the same manner as in "Fractional Ester, Example 1, preceding. Such procedure is illustrated by the following examples:

TOTAL ESTER Example 1 One pound mole of the fractional ester described under the preceding heading marked Fractional Ester, Example 1 is mixed with one pound mole of oleic acid and one-half of 1% oftoluene sulfonic acid and an amount of xylene equivalent to approximately fifty percent by volume of the reaction mixture. Such mass is refluxed with an appropriate trap for the removal of one pound mole of water at a temperature of approximately 165 to 233 C. Time required is usually three to ten hours. The resultant mass is adarlg, rather thick, viscous liquid.

TOTAL ESTER Example 2 The same procedure is followed as in the preceding example, except that instead of using a fractional ester, exemplified by Example 1, one employs instead a fractional ester of the kind exemplified by the products described under the headings Fractional Ester, Example 2 or Fractional Ester, Example-3.

TOTAL ESTER Ewample 3 Stearic acid is substituted for oleic acid, in Examples land 2, preceding.

TOTAL ESTER Example 4 Ricinoleic acid is substituted for oleic acid,.in

Examples 1 and 2, preceding.

"TOTAL ESTER Example 5 A naphthenic acid (or mixture of naphthenic give the fractional ester. Reference is also made to the earlier reactions indicating the combina? tion of the total ester with pyridine or a C-linke'd methyl-homolog of pyridine. H PYRIDINIUM HALIDE Example 1 I One pound mole of the total ester described. in. Examplel, preceding, is refluxed with constant stirring with several pound moles, for example, four to six, of technically pure pyridine. The

reaction is conducted from approximately 1 hour; to 20 hours, at a temperature in excess of C.,;or thereabouts, until reaction is complete.

Completeness of the reaction can be determined. by distilling the uncombined pyridine from a sample and noting, by difference, the percentage of pyridine, which has been combined. Another Chlorine I I-H2O.C 0114050 0021140 00 can" PYRIDINIUM HALIDE Example 2 The same procedure is followed as in immediately preceding Example 1, except that a total ester, exemplified by Examples 2, 3, 4, or 5, preceding, is used instead of the total ester exemplified by Example 1, preceding.

PYRIDINIUM HALIDE Example 3 The same procedure is followed as in the first two examples, but instead of using technically pure pyridine, one employs a commercial pyridine, in which there is present some monomethylpyridine and dimethylpyridine in addition to unsubstituted pyridine.

It is to be emphasized that all of the products herein contemplated are water-dispersible, or at least, produce a colloidal sol or show a distinct hydrophile property, after reaction with pyridine or pyridine homolog. The reactants, prior to such procedure, are not water-soluble. The compounds contemplated vary from fairly viscous liquids to semi-solids and solids. When produced in either glass or iron vessels, they invariably have a dark amber color.

In summary, then, the herein contemplated compound may be indicated by the following structural formula:

halogen y in which R20 is an alkoxy radical selected from the group consisting of -C2H4O- and -C3HcO- radicals; n is a small whole number varying from 1 to 3; OC.R3 is the acyl radical of a low molecular weight monocarboxy acid having not more than 3 carbon atoms, in which an alpha-hydrogen atom has been removed, linked to the nitrogen of the radical NER4 through its alpha carbon atom; NERA represents a radical of a heterocyclic compound of the pyridine series selected from the group consisting of pyridine and C-linked methyl homologs of pyridine; R5 is a radical selected from the class consisting of methylene and hydrocarbonsubstituted methylene radicals having not over 7 carbon atoms; R6 is a member of the class consisting of hydrogen atoms and alkyl radicals having not over 8 carbon atoms; the phenolic residues are substituted monocyclic phenol radicals having two of the three reactive 2, 4, 6 positions substituted by two alkyl side chains, of which at least one contains at least three carbon atoms and the longest of which does not contain more than 8 carbon atoms; and (RcOmOCRn is a radical in which R20 and n have their prior significance, and RvCO is the acyl radical of a monocarboxy acid having at least 8 and not more than 32 carbon atoms. I

The new materials or compositions herein described, are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like; as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various mineralsjfo'r flocculation and coagulation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes, and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive, as far as industrial application goes, although the most important use of our new material is as a demulsifier for water-in-oil emulsions, and more specifically, emulsions of water or brine in crude petroleum. 7

We have found that the chemical compounds herein described which are particularly desirable for use as demulsifiers, may also be used as a. break inducer in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension de-' pressa'nts in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhaust oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil fromsubterranean strata, reference is made to the procedure described in detail in U. S. Patent No.-

2,226,1l9, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants, in combination with mineral acid for acidization of oil-bearingstrata, reference is made to U. S. Patent No.

2,233,383, dated February 25, 1941, to De Groote and Keiser.

The new compounds herein described are of utility, not only for the purposes -specifically enumerated in detail, but they also find application in various other industries, processes, and for various uses where wetting agents of the conventional type are used. As to some of such addi semi-solid, probably should be referred to as a tacky sub-resin or a tacky resin. The phenol aldehyde condensate, particularly when'derived from formaldehyde, shows not only viscosity, but tackiness approaching or actually in the stringy state. This particular property is usually enhanced after conversion into a pyridinium compound. This enhancement applies usually to both the stringy character and the resinous character. Such change appears to be imparted by the facts that the large molecular structure still exists, but in addition, an ionic structure has been superimposed on the somewhat unusual molecular structure. This ionic structure naturally acts the same as such structure would act in an ordinary inorganic salt crystal. One result of such peculiarity is, that sometimes water solubility may be obscured. For instance, tests have been indicated previously which are employed to show when the reaction with pyridine has gone to completion. On completion, the structure of the resultant may be so resinous and so tacky, that it shows a very slow rate of solubility in water. Thus, a test may, at first sight, indicate the product is still water-insoluble, whereas, it is actually water-soluble, or at least, self-emulsifiable. To guard against such possible error, it is well to take a small amount of the reaction mass and reflux it with an excess of water, or better still, dissolve the reaction mass by warming in methyl alcohol and then dilute with an excess of water.

Attention is directed to our co-pending applications for patent Serial Nos. 586,262, 586,263, 586,266 and 586,267, all filed April 2, 1945, and all issued November 4, 1947, as Patents Nos. 2,429,996, 2,429,997, 2,430,000 and 2,430,001, respectively, and application Serial No 630,973, filed November 26, 1945,

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A hydrophile chemical compound of the formula:

halogen O (R ),,.0 CR

alkylalkylin which R20 is an alkoxy radical selected from the group consisting of -C2H4O-- and -C3Ha0- radicals; n is a small whole number varying from 1 to 3; OC.R3 is the acyl radical of a low molecular weight monocarboxy acid having not more than 3 carbon atoms, in which an alpha-hydrogen atom has been removed linked to the nitrogen of the radical NR4 through its alpha carbon atom; Nil-t4 represents a radical of a heterocyclic compound of the pyridine series selected from the group consisting of pyridine and C-linked methyl homologues of pyridine; R5 is a radical selected from the class consisting of methylene and hydrocarbon substituted methylene radicals having not over 7 carbon atoms; R6 is a member of the class consisting of hydrogen atoms and alkyl radicals having not over 8 carbon atoms; the phenolic residues are substituted monocyclic phenol radicals having two of the three reactive 2, 4, 6 positions substituted by 2 alkyl side chains, of which at least one contains at least 3 carbon atoms and the longest of which does not contain more than 8 carbon atoms; and (R20)1L.OCR7 is a radical in which R20 and it have their prior significance and RC0 is the acyl radical of a monocarboxy acid having at least 8 and not more than 32 carbon atoms.

2. The compound of claim 1, wherein the halo- 4 gen is chlorine.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,917,258 Harris July 11, 1933 1,970,578 Schoeller Aug. 21, 1934 2,023,075 Harris Dec. 3, 1935 2,299,782 Allen et a1 Oct. 27, 1942 2,306,775 Blair Dec. 29, 1942 

1. A HYDROPHILE CHECMICAL COMPOUND OF THE FORMULA: 